Metal-containing polyazo dyestuffs



plex compounds.

group. i

United States Patent O" 2941,9911 METAL-CONTAINING POLYAZO DYE'STUFFSHans-Rudolf Byland, Riehen, near Basel, Switzerland, as-

signor, by mesne assignments, to Saul & Co., Newark, N.J., as nominee ofFidelity Union Trust Company, executive trustee under SandozTrust NoDrawing. Filed Oct. 7, 1955, Ser. No. 539,257 Claims priority,application Switzerland 12, 1954 6 Claims. or. 260-145) u The presentapplication is a continuation-in-part application to my co-pendingapplication Ser. No. 491,202, filed on February 28, 1955 (now US. PatentNo. 2,803,- 624) and relates to new metal, especially copperandnickel-containing polyazo dyestufls.

' The co-pending application Ser. No. 491,202 is concerried with theembodiments of metal-containing, especially copperand nickel-containingpolyazo dyestuffs which, in the metal-free state,correspond to theformula wherein x stands for OH, OCH OC H or COOH, R stands for hydrogenor a radical of the aliphatic, alicyclic, araliphatic or aromaticseries, R stands for a monoor binuclear radical of the benzene series, ystands for the radical of a hydroxynaphthalene compound and is linked tothe respective -N=N- group in ortho-position to the hydroxy group ofsaid hydroxynaphthalene compound, radicals of the composition A beingincluded, and wherein -OH adjacent to R is located in ortho-position tothe respective --N=N group. p

It has now been found that polyazo dyestufis of the general Formula Iwhich carry a carboxylic acid group; adjacent to or in' place of the OHgroup located on the radical R in ortho-position to the respective N'=Ngroup, can also be converted into valuable metal com- Moreover thesymbol x, in the new metalliferous polyazo dyestufis, may represent aOCH .COOH f:

The new metalliferous polyazo dyestuffs correspond,

the metal free state, to the general formula 2,941,991 Patented June 21,1960 "ice phatic, alicyclic, araliphatic or aromatic series, x standsfor OH, 0OH 0C H --COOH or -OCH .COOH

y stands for the radical of an hydroxynaphthalene compound and is linkedto the respective -N=N- group 7 further substituents commonly used inazo dyestuiis.

The process of preparation of the new metalliferous polyazo dyestuifsconsists in treating polyazo dyestuffs which correspond to the generalFormula II, wherein R, x, y, a, b and A have the significances recitedin the foregoing paragraph, with metal-yielding, preferably copperornickel-yielding agents. 1 I

The metallization of the polyazo dyestuflfs defined in the foregoingparagraph is carriedout preferably with copperor nickel-yielding agents,e.g. with copper formate, copper acetate, copper sulfate, or with thecorresponding nickel compounds. The metallizing operation may beeifected in several different ways, for example byyheating the dyestuffswith copper salts in a weakly acid to alkaline medium, if desired withpressure applied, and/or in the presence of ammonia and/ or organicbases, or in aqueous solutions of alkaline salts of low-molecularaliphatic monocaroxylic acids. If the polyazo dyestuffs contain alkoxygroups capable of being metallized, the metallization must be conductedwith simultaneous splitting of these groups.

. soluble, for example carboxylic acid, sulfonic acid, sultonic acidamide and lower alkylsulfonyl groups. a Metali for cellulosic fibres.

liferous polyazo dyestufi's which are only poorly soluble in warm water,often possess particularly good aflinity facility at temperatures above100 and under pressure.

Of the substituents capable of being metallized the most important arethe OH, OCH and COOH groups. In the case of the OCH COOH group 'thejentire CH COOH radical is split off in the de-alkylating metalliZ ationaccording to the present invention, so that the use of polyazo dyestuffscontainingsuch groups'often proves uneconomical. The new metalliferouspolyazo dyestufis are characterizedby good compatability with salt andby the bright, deep navy blue shades of their dyeings on cotton andfibres of regenerated cellulose. The dyeings are dischargeable andpossess very good light fastness and goodto very good fastness towashing and water. Dyeings aftertreated with polyalkylene polyaminepreparations containing copper, if desired in complex combination, havea particularly high standard of tastness. In addition the new dyestuffsreserve acetate rayon, and are also suitable for use in textileprinting.

The invention is illustrated by the following examples. All parts andpercentages are by weight; temperatures are given in degrees centigrade.

EXAMPLE 1 107.8 parts of the trisazo dyestufi obtained by coupling 1 molof tetrazotized 4.4'-diamino-3.3-dimethoXy-1.1'-di- These dyestuffs canbe dyed with.

and is then filtered off and dried. It is a dark powder phenyl with 1mol of 1-hydroxynaphthalene-3.Z-disulerated cellulose in navy blueshades which have outstandfonic acid and 1 mol of1-(2-carboxyl-4'-nitro)-pheny1- ing fastnessproperties.azo-2-phenylamino-5-hydroxynaphthalene-7-sulfonic acid The newnickel-containing trisazo dyestufi corresponds are suspended with 100parts of diethanolamine, parts to the formula -SO3H 503's o- 1 i ofsodium carbonate and 50 parts of ammonia 25% in EXAMPLE 3 2000 parts ofwater. The suspension is heated'to 90",

at which point the trisazo dyestulf enters into partial solution;'A-solution of 76 parts of crystallized copper sulfate and 200 parts ofammonia is added dropwise to the mass at 90* in the course of minutes.The mass isboiled for 24 hours at the reflux, during which time thecopper complex compound, upon formation, enters into complete solution.The solution is subsequently allowed to cool; the cupriferous trisazodyestulf is precipitated by an addition of 160 parts of sodium chloride,

105 parts of the trisazo dyestuff obtained byvcoupling 1 mol oftertrazotized 4.4'-diarnino-3.3-dihydroxy-1.1-difonic acidand 1 moi-of1-(2-carboxy-4'-nitro)-phenyl copper sulfate are added to thesuspension, and the mass is heated for 24 hours at the reflux underconstant agitathe precipitated copper complex compound of the trisazo 30dyestufi is filtered as and dried. The cupriferous trisazo navy blueshades which have remarkable fastness propdyesmfi displays the SameproPgrfie's a the Idem-cal erties copper complex compound described nExample A very similar dyestulf' is obtained when l-hydroxy- EXAMPLE 4naphthalene-3.G-disulfonic acid is employed in place of1-hydroxynaphthalene-3.8-disulfonic acid for the produc- When 79 partsof crystallized nickel sulfate are added which dissolves in Waterwith adeep blue colouration, and dyes cotton and fibres of regeneratedcellulose in phenyl with 1 mol'of 1-hydroxynaphthalene-3.S-disul--azo-2phenylamino-5-hydroxynaphthalene-7-sulfonic acid 7 are suspended in400 parts of molten sodium acetate lcon- I 25 taining water ofcrystallization. 80 parts of crystallized tion. It is subsequentlydiluted with 2000 parts of water;

tion of the starting product to the suspension described in Example 3 inplace of The new copper-containing trisazo dyestuffs correspond 80 partsof crystallized copper sulfate, and .theoperating to the formulaeprocedure described in that example'is followed in all I H033 0-ou o andHots so311 -Cu t O EXAMPLE 2 other particulars, a nickelif erous trisazodyestuff is ob- 107.8 parts of the trisazo dyesmfi used as Starting 1tamed WhlCh'haS the same propert1es as the identical nickel complexcompound described in Example 2. product in Example 1, paragraph 1, aredissolved with V r 100 parts of pyridine, 15 parts of sodium carbonateand Ihe table which f i q further 50 parts of ammonia 25% in 2000 pansof Waten To hferous polyazo dyestuffs which in their non-metallized thissolution is added in the course of 30 -minutes a form crrespond to thegeneral formula solution of 79 parts of crystallized nickel sulfate N Nt (NiSOg-6Hz0) and 400 .parts of ammonia 25%; the W T whole is'thenboiled at the reflux for 24 hours. The v 1 solution is subsequentlycooled, the nickel complex oorn- I pound of the trisazo dyestufi thusformed precipitated In column (2) of the table the significance of x isinby an addition of 300 parts of sodium chloride, filtered V dicated.'i'he monoazo compound (II) forrrung the base oil and dried. Thenickeliferous trisazo dyestufl is a of one of the radicals y and thesecond azo'component dark powder which dissolves in water to give deepblue- "forming the base of the other y radical are named in colouredsolutions. It dyes cotton and fibres of regen- 5 columns (3) and (4)respectively. In colunm -(5) the S 11 H O as H0318 (5 V (I) (Bu--EXAMPLE 19 HOaS- SO3H V HOsS l (t at. 6 5..

' It is evident fromthe foregoing examples that'the number of atoms ofmetal in the molecule of the dyestufi's is equal to the number of azo(--N =N--) groups.

' EXAMPLE 32 100 pa1ts of cotton, wetted out: in hot water, are enteredinto a dyebath at 40 containing a solution of 1.5 parts of the 'dyestuffproduced according toExample 1, paragraph 1, and 10 parts of Glauberssalt in 3000 parts of soft water. The bath is heated to 100 in thecourse of about 30 minutes during which time 20 parts of Glaubers saltare added in portions. The dyeing process is continued for minutes at100, after which a further 10 parts of Glaubers salt are added; The bathis then allowed to cool to about 50 in 15-20 minutes, when the dyedcotton is removed, rinsed and dried.

Fibres of regenerated cellulose are dyed in the same way.

EXAMPLE 33 15 parts of the dyestuff described in Example 1, paragraph 2,are boiled with 100 parts of urea and 45 parts of triethanolamine in 360parts of water. The solution is then given 400 parts of tragacanth 6%,parts of sodium phosphate, 40 parts of an anionic wetting agent and 10parts of an antifoaming agent. A fabric of viscose rayon is printed withthis printing paste; the printed fabric is dried, steamed for 45-60minutes, and rinsed. After a 15 minute aftertreatment at 60 with 1 g./l.of a polyalkylene polyamine preparation containing copper salt, theprinted fabric is again rinsed and dried.

EXAMPLE 34 22.5 parts of the cupriferous tris-azo dyestuff obtainedaccording to Example 1, paragraph 1, are dissolved in 1000 parts ofboiling distilled water. The solution is allowed to cool and applied inthe cold state from a padder on a cotton fabric. With a take-up of 80%(calculated on the weight of the material), a navy blue dyeing isobtained.

Fixation of the padded dyestuff on the cotton fibre is efiected bytreatment in a steam or hot salt bath, e.g.

with 20 grams of common salt per litre. The material is subsequentlyrinsed and dried.

What is claimed is:

l. A water-soluble substantive metal-containing polyazo dyestufi whereinthe metal is selected from the class consisting of copper and nickel,and which, in the metal- I free state, corresponds to the formula I) a Vwherein R stands for a member selected from the group consisting ofhydrogen and aliphatic, alicyclic, araliphatic and mononuclear aromaticradicals, x stands for a member selected from the group consisting ofOH, OCH;;, OC H COOH and OCH .COOH, y stands .for the radical of anhydroxy-naphthalene compound linked to the adjacent -N=N-- group inorthoposition to the hydroxy group and is selected from the groupconsisting of a radical of an unsubstitutedhydroxynaphthalenemonosulfonic acid, a radical of an unsubstitutedhydroxynaphthalenedisulfonic acid, a radical of an unsubstitutedhydroxynaphthalenetrisulfonic acid, and a radical of composition A, astands for a member selected from the group consisting of hydrogen andCOOH, b stands for COOH when a is hydrogen, and stands for OH when a isCOOH, 0 stands for a member selected from the group consisting ofhydrogen, chlorine, nitro, SOgII, SO NH SO .NH.lower alkyl, SO .NH.-lower hydroxyalkyl, SO .NI-I.lower alkoxyalkyl and SO .lower alkyl, andwherein the total number of sulfonic acid groups contained in thepolyazo dyestufi molecule amounts to at least 3 and at most 4, and thenumber of atoms of metal in said molecule is the same as the number of--N=N- groups.

2. The water-soluble substantive cupriferous polyazo dyestuff whichcorresponds to the formula I 11013 o--ou (111-0 3. The water-solublesubstantive cupriferous polyazo dyestufi' which corresponds to theformula 15 4. The water-soluble substantive cupriferous polyazo dyestfiwhich corresponds to the formula SOrH N 5. The water-soluble substantivecupriferous polyazo 6. The water-soluble substantive cupriferous polyazo55 dyestufi which corresponds to the formula N IFQNO:

I nmswsozn HOaS N-u-o =0 l i (Ju- S0:NH1

References Cited in the file of this patent 2,644,812 Ruckstuhl et a1.July 7, 1953 UNITED STATES PATENTS 2,842,539 Byland July 19 2,417,306Krebser et a1. Mar. 11, 1947 OTHER REFERENCES 2,507,754 Bossard et a1May 16, 1950 Venkataraman, Synthetic Dyes, vol. II, pages 1290 2,638,468Wehrli May 12, 1953 and 1350.

1. A WATER-SOLUBLE SUBSTANTIVE METAL-CONTAINING POLYAZO DYESTUFF WHEREINTHE METAL IS SELECTED FROM THE CLASS CONSISTING OF COPPER AND NICKEL,AND WHICH, IN THE METALFREE STATE CORRESPONDS TO THE FORMULA